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Synthesis, characterization, luminescence

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Cite this: Dalton Trans., 2023, 52,

properties and deciphering the role of a terpyridyl-
14027 imidazole based ligand in the dissimilar
luminescence sensitization of ternary
lanthanide(III) tris-(β-diketonate) complexes†
Toushique Ahmed, Amit Chakraborty, Animesh Paul and Sujoy Baitalik *

We designed four ternary lanthanide tris-(β-diketonate) complexes of the form [Ln(tta)3(tpy-HImzphen)],

Received 2nd June 2023,
Accepted 6th September 2023
DOI: 10.1039/d3dt01701j
rsc.li/dalton
where Ln = LaIII, EuIII, SmIII and TbIII; tta = (2-theonyltrifluoroacetonate) and tpy-HImzphen = 2-(4-
[2,2’:6’,2’’]terpyridin-4’-yl-phenyl)-1H-phenanthro[9,10-d]imidazole. All the complexes have been thoroughly
characterized by standard analytical tools and spectroscopic techniques including single crystal X-ray diffrac-
tion. In situ generation of the complexes was also monitored via absorption and emission spectroscopy upon
incremental addition of the respective lanthanide precursor {Ln(tta)3(H2O)2} to the dichloromethane solution
of the terpyridyl-imidazole ligand. The photophysical behaviors of all the complexes were thoroughly investi-
gated via absorption and both steady-state and time-resolved emission spectroscopic techniques. The emis-
sion spectral measurements were carried out at both room temperature and 77 K to understand the de-
activation dynamics of the excited states and elucidate the distinctive luminescence responses from the four
lanthanide metal ions owing to the introduction of the terpyridyl-based ancillary ligand.

Introduction applications.16,17 Several strategies have been adopted to over-

Appropriate design of trivalent lanthanide complexes is of
pivotal importance for the development of potential light har-
vesting materials by taking advantage of their fascinating
photo-luminescence properties.1–4 Lanthanide complexes
exhibit typical narrow monochromatic emission (high colour
purity) together with large pseudo-Stokes shifts and long
excited-state lifetimes which make them fundamentally dis-
tinctive from other regular fluorescent probes. This is because
of the presence of deep-seated 4f electrons which remain
unperturbed in the presence of an external ligand field. These
properties make lanthanide complexes potential building
blocks in diverse fields of applications such as laser sources,
luminescent sensors, bio-imaging, drug delivery and medical
diagnosis, to name a few.5–15 But because of the symmetry for-
bidden characteristics of intra-configurational f–f transitions,
lanthanide complexes usually exhibit very weak luminescence
which is the major deterrent to their potential light harvesting
Inorganic Chemistry Section, Department of Chemistry, Jadavpur University, Kolkata
700032, India. E-mail: sbaitalik@hotmail.com, sujoy.baitalik@jadavpuruniversity.in;
Tel: +913324146666
† Electronic supplementary information (ESI) available: Tables S1–S4 and
Fig. S1–S16. CCDC 2255186. For ESI and crystallographic data in CIF or other
electronic format see DOI: https://doi.org/10.1039/d3dt01701j
come the discrepancies and improve the luminescence charac-
teristics of the lanthanides.1,2
Among the different strategies, anchoring of judicially
chosen light harvesting organic chromophores with high
molar absorption coefficients (ε > 10 000 M−1 cm−1) could
circumvent this problem.6,18 The light absorbed by the organic
chromophores could in turn excite the lanthanide core. This
‘antenna effect’ offers an indirect sensitization of the LnIII ion
and often provides substantial enhancement of luminescence
intensity, quantum yield and lifetime.4,8,19–21 Thus, the
tailored design of appropriate ligands could give rise to
lanthanide complexes with enhanced luminescence
characteristics.22,23 It is worth mentioning that the ligand(s)
being employed should possess appropriate singlet and triplet
energy levels that should match the lowest excited state of the
corresponding trivalent lanthanide ion in accordance with
Reinhoudt’s and Latva’s empirical rules.1,2,24 The photo-
luminescence generated from the trivalent lanthanide ions is
proportional to the efficacy of energy transfer from the
antenna/sensitizer ligand. In this regard, β-diketonate ligands
have been widely employed as these ligands not only provide
charge balance to the metal ions but also sensitize the lantha-
nide center creating an innocent coordination environment.25
Additionally, one can modulate the energy levels of the
β-diketonates upon substitution of the appropriate moiety or

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Scheme 1 The ligand, lanthanide precursors and the resulting four lanthanide complexes Ln(tta)3(tpy-HImzphen) (1–4) in the present study.
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by incorporating another chromophoric segment to cater to
the need.25–27 In spite of presenting themselves as one of the
best candidates for effective sensitization of the lanthanide
ions, it has been noted that the β-diketonate ligands lack
selectivity towards lanthanide ions in terms of sensitization,
thereby only yielding monochromatic luminescence as antici-
pated for the respective lanthanides.1–4
The primary objective of the present work is to utilize poly-
pyridine-based ancillary ligands in combination with
β-diketonates to modulate the photophysics in general and
luminescence characteristics in particular of the resulting
lanthanide complexes. Presently, we have focussed our interest
on three lanthanide ions (viz., EuIII, SmIII, and TbIII) along
with LaIII itself in terms of having the facility to measure the
photophysical properties in the visible domain. Upon going
through the literature, it appears that among the polypyri-
dines, bidentate bipyridine-type chelating units are mostly
employed for the designing of mixed-ligand lanthanide
complexes.28–36 By contrast, the systems comprising tridentate
terpyridine-type chelating motifs together with β-diketonates
are relatively sparse.16,37–41 Our research group has been
working for the last one decade on the design and synthesis of
a wide variety of terpyridine-type ligands covalently coupled
with both electron-donating and electron-withdrawing groups
as well as incorporating different types of aromatic and hetero-
aromatic moieties.42,44,46 We also thoroughly investigated the
ground- and excited-state photophysical and electrochemical
behaviours of 4d and 5d metals {mainly Ru(II) and Os
(II)}.43,45,47–49 After careful scrutiny of the structure and the
absorption and emission spectral behaviors, we anticipated
that one of our previously reported terpyridyl-imidazole based
receptors, viz. 2-(4-[2,2′:6′,2″]terpyridin-4′-yl-phenyl)-1H-phe-
nanthro[9,10-d] imidazole (tpy-HImzphen), might be a good
choice to serve our need. The said terpyridine ligand coupled
with a phenyl-phenanthro-imidazole spacer appropriately
adjusts its excited state energy position so that effective sensit-
ization of the lanthanide core could be feasible. Additionally,
we have chosen 2-theonyltrifluoroacetone (Htta) as the favour-
able β-diketonate because of the presence of low energy C–F
bonds which induce rigidity and thereby limit the non-radia-
tive deactivation of LnIII excited state energy as compared to
high energy oscillators, viz., C–H, N–H, and O–H bonds.18,50
Herein, we report the synthesis of four lanthanide com-
plexes of the form Ln(tta)3(tpy-HImzphen) (Ln = LaIII, EuIII,
SmIII and TbIII) and their thorough characterization via stan-
14028 | Dalton Trans., 2023, 52, 14027–14038
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dard analytical tools including single crystal X-ray diffraction
(Scheme 1). The photophysical properties of all the complexes
were thoroughly investigated via absorption and both
steady-state and time-resolved emission spectroscopic
techniques at room temperature and 77 K to understand the
deactivation dynamics of the excited states and elucidate the
distinctive luminescence responses of the lanthanide
complexes.
Experimental section
Materials
2-Theonyltrifluoroacetone (Htta) and all the lanthanide salts
containing either chloride or nitrate counter anions were pur-
chased from Merck. The ligand precursors, 4′-( p-formyl
phenyl)-2,2′:6′,2″-terpyridine (tpy-PhCHO) and 9,10-phenan-
threnedione, were synthesized by following the reported litera-
ture method.51 All the photophysical measurements were
carried out in dry and decontaminated solvents. We purified
and distilled the solvents following standard literature
procedures.52
Synthesis of the ligand and lanthanide precursors
Details of the synthesis and characterization of the four
lanthanide precursors of the type [Ln(tta)3(H2O)2], Ln = La, Eu,
Sm, and Tb53, as well as our previously published terpyridyl-
imidazole ligand44 are given in the ESI.†
Synthesis of the lanthanide complexes, Ln(tta)3(tpy-
HImzphen)
A general synthetic protocol has been adopted for the syn-
thesis of all the four lanthanide complexes, Ln(tta)3(tpy-
HImzphen), LnIII = LaIII (1), EuIII (2), SmIII (3) and TbIII (4). To
a stirred suspension of tpy-HImzphen (20 mg, 0.038 mmol) in
a chloroform–methanol (1 : 1 v/v) mixture, an equimolar
amount of the respective Ln(tta)3(H2O)2 precursor complex was
added and stirred magnetically for 6 h at 60 °C. The resulting
mixture was vacuum-dried and then dissolved in a small
amount (∼5 mL) of dichloromethane and layered with hexane.
After keeping for a few hours, the microcrystalline solid that
was deposited was filtered and then dried in vacuum
desiccators.
La(tta)3(tpy-HImzphen) (1). La(tta)3(H2O)2 (32 mg,
0.038 mmol); yield: 36 mg (72%). Anal. calcd for
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C60H35F9S3O6N5La: C, 54.26; H, 2.66; N, 5.27. Found: C, 54.17;
H, 2.56; N, 5.21. FT-IR: ν (in cm−1) = 1535, 1605, 3250.
MALDI-TOF (DCTB, positive mode): m/z = 1106.17 (100%) [M −
tta]+. 1H NMR (DMSO-d6, 400 MHz, δ/ppm): 13.66 (s, 1H, NH
(imidazole)), 8.88 (d, 2H, J = 5.48 Hz, H12), 8.85 (s, 2H, H9),
8.81 (d, 2H, J = 5.3 Hz, H8), 8.72 (d, 2H, J = 8.3 Hz, H5), 8.63 (t,
2H, J = 8.0 Hz, H15), 8.56 (d, 2H, J = 8.3 Hz, H11), 8.22 (d, 2H, J
= 7.4 Hz, H10), 8.06 (d, 2H, J = 5.9 Hz, H6), 7.80 (m, 6H; H2,
H4), 7.74 (d, 2H, J = 8.0 Hz, H14), 7.67 (d, 2H, J = 8.0 Hz, H13),
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7.56 (t, 2H, J = 6.0 Hz, H7), 7.12 (t, 3H, J = 4.0 Hz, H3), 6.18 (s,
3H, H1 methine).
Eu(tta)3(tpy-HImzphen) (2). Eu(tta)3(H2O)2 (33 mg,
0.038 mmol); yield: 37 mg (75%). Anal. calcd for
C60H35F9S3O6N5Eu: C, 53.74; H, 2.63; N, 5.22. Found: C, 53.67;
H, 2.58; N, 5.18. FT-IR: ν (in cm−1) = 1534, 1607, 3105.
MALDI-TOF (DCTB, positive mode): m/z = 1120.143 (100%) [M
− tta]+ 1H NMR (DMSO-d6, 400 MHz, δ/ppm): 13.66 (s, 1H, NH
(imidazole)), 8.85 (s, 2H, H12), 8.81 (d, 2H, J = 8.0 Hz, H9), 8.78
(t, 2H, J = 4.0 Hz, H8), 8.70 (t, 2H, J = 8.0, H5), 8.63 (t, 2H, J =
8.0 Hz, H15), 8.55 (d, 2H, J = 8.0 Hz, H11), 8.22 (d, 2H, J = 8.0
Hz, H10), 8.06 (d, 2H, J = 8.0 Hz, H6), 7.66 (d, 2H, J = 4.0 Hz,
H14), 7.56 (m, 2H, H13), 7.44 (s, 2H, H7), 7.36 (s, 3H, H4), 6.48
(s, 3H, H3), 6.36 (s, 3H, H2), 4.51 (s, 3H, H1 methine).
Sm(tta)3(tpy-HImzphen) (3). Sm(tta)3(H2O)2 (32 mg,
0.038 mmol); yield: 31 mg (63%). Anal. calcd for
C60H35F9S3O6N5Sm: C, 53.80; H, 2.63; N, 5.23. Found: C, 53.72;
H, 2.54; N, 5.18. FT-IR: ν (in cm−1) = 1536, 1609, 3080.
MALDI-TOF (DCTB, positive mode): m/z = 1118.18 (100%) [M −
tta]+ 1H NMR (DMSO-d6, 400 MHz, δ/ppm): 13.66 (s, 1H, NH
(imidazole)), 8.85 (s, 2H, H12), 8.82 (m, 2H, H9), 8.78 (s, 2H,
H8), 8.70 (s, 2H, H5), 8.63 (t, 2H, J = 8.0 Hz, H15), 8.56 (d, 2H, J
= 8.0 Hz, H11), 8.22 (d, 2H, J = 8.0 Hz, H10), 8.13 (s, 3H, H1
methine), 8.06 (d, 2H, J = 8.0 Hz, H6), 7.85 (t, 2H, J = 4.0 Hz,
H14), 7.77 (d, 2H, J = 8.0 Hz, H13), 7.67 (d, 2H, J = 4.0 Hz, H7),
7.55 (t, 3H, J = 6.44 Hz, H2), 7.32 (s, 3H, H3), 7.21 (s, 3H, H4).
Tb(tta)3(tpy-HImzphen) (4). Tb(tta)3(H2O)2 (33 mg,
0.038 mmol); yield: 33 mg (67%). Anal. calcd for
C60H35F9S3O6N5Tb: C, 53.46; H, 2.62; N, 5.20. Found: C, 53.36;
H, 2.57; N, 5.13. FT-IR: ν (in cm−1) = 1538, 1607, 3104.
MALDI-TOF (DCTB, positive mode): m/z = 1126.01 (100%) [M −
tta]+. 1H NMR (DMSO-d6, 400 MHz, δ/ppm): 95.20 (s, 3H, H1
methine), 29.00 (s, 3H, H2), 13.76 (s, 1H, NH(imidazole)),
12.16 (s, 3H, H3), 8.97 (m, 2H, H12), 8.95 (s, 2H, H9), 8.86 (d,
2H, J = 4.52 Hz, H8), 8.79 (d, 2H, J = 8.0 Hz, H5), 8.73 (d, 2H, J
= 8.0 Hz, H15), 8.65 (d, 2H, J = 8.0 Hz, H11), 8.32 (d, 2H, J = 8.0
Hz, H10), 8.08 (t, 2H, J = 8.0 Hz, H6), 7.84 (m, 2H, H14), 7.72
(m, 2H, H13), 7.58 (m, 2H, H7), 6.58 (s, 3H, H4).
Results and discussion
Synthesis and characterization
All the four LnIII complexes were synthesized in a straight-
forward manner upon refluxing a 1 : 1 molar ratio of the terpyr-
idyl-imidazole ligand with the respective lanthanide precursor,
Ln(tta)3(H2O)2, in a chloroform–methanol (1 : 1 v/v) mixture.
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The complexes were finally purified upon diffusing hexane
into their dichloromethane solutions at ambient temperature
and the products were obtained in reasonably good yields. All
these complexes were thoroughly characterized by elemental
analysis, FT-IR spectroscopy, 1H NMR spectroscopy, matrix-
assisted laser desorption ionization time of flight
(MALDI-TOF) mass spectrometry and thermogravimetric ana-
lysis. The detailed FT-IR analysis is provided in Table S1 and
Fig. S1–S4, ESI.†
1
H NMR spectra
The 1H NMR spectra of all the four complexes along with their
tris(β-diketonate) precursors and the terpyridyl-imidazole
ligand were recorded in DMSO-d6. The 1H NMR spectra of 1
and 4 together with tentative assignments of all the proton
resonances are presented in Fig. 1, 2 and Table S2 (ESI†),
while those of the remaining two complexes (2 and 3) are pro-
vided in Fig. S5 and S6 (ESI†). Upon coordination of the La
(tta)3(H2O)2 precursor, the protons associated with tta moieties
are found to move towards the up-field region in the resulting
complex (Fig. 1c). Tpy-HImzphen protons, on the other hand,
undergo only a minor up-field shift accompanied by a change
in the multiplicity of the signals compared with their free
form.44 The protons in the remaining complexes (2, 3 and 4)
experience unpredictable paramagnetic shifts together with
the change in multiplicity. The tpy-HImzphen protons in these
complexes also do not experience a remarkable alteration in
their chemical shift values. By contrast, the protons associated
with the tta moieties experience a notable paramagnetic up-
field shift, as shown in Fig. 2 and Fig. S5, S6 (ESI†). The effect
is quite marked with the TbIII complex (Fig. 2) relative to EuIII
and SmIII complexes (Fig. S5 and S6, ESI†).
Mass spectra
Matrix-assisted laser desorption ionization time of flight mass
spectra (MALDI-TOF MS) of all the four complexes are
recorded in dichloromethane to further confirm the structure
of the complexes in the solution phase. A representative mass
spectrum of complex 2 together with the experimental and
simulated isotopic distribution patterns is presented in Fig. 3,
while the spectra of the remaining complexes are provided in
Fig. S7–S9, ESI.† A good correlation between the experimental
and simulated isotopic patterns is observed for all cases. Each
of the four complexes displays one intense peak with its m/z
value spanning in the range of 1106.17–1126.01. The separ-
ation between successive lines in both the experimental and
simulated isotopic patterns is found to be 1.0 Da and thus
corresponds to the mono-positive cations of the type [{Ln
(tta)3(tpy-HImzphen)}-(tta)]+.24
Thermal stability of the complexes
In order to investigate the thermal stability of the complexes,
we also performed their thermogravimetric analysis under a
nitrogen atmosphere within the temperature range of
30–800 °C and at a heating rate of 10 °C m−1. All of the four
complexes exhibit nearly similar patterns in terms of both
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Fig. 1 400 MHz 1H NMR spectra of Htta (a), La(tta)3(H2O)2 (b) and La(tta)3(tpy-HImzphen) (1) (c) in DMSO-d6.
decomposition and weight loss (Fig. 4). The complexes showed
a minor weight loss at ∼190 °C and two major weight losses at
∼290 °C and ∼555 °C but did not show any weight loss at
∼100 °C, unlike their respective metal precursors, which
suggests that the complexes are amorphous in nature and lack
any coordinated or lattice-trapped water molecule (Fig. 4). The
minor weight loss at ∼190 °C may be attributed to the loss of
moisture within the sample. At the onset temperature of
∼290 °C, decomposition starts and continues up to ∼400 °C
(up to ∼50% weight loss), which can be ascribed to the loss of
ancillary ligands and tta moieties. The second major weight
loss starts at ∼555 °C and continues thereafter probably
because of the formation of metal oxides. Hence, it can be con-
cluded that the complexes have adequate thermal stability up
to ∼300 °C.
X-ray crystallography
We were curious to know the unambiguous structure of the
synthesized complexes through single crystal X-ray crystallogra-
phy. Despite numerous sincere efforts, we were unable to
obtain suitable single crystals from the synthesized complexes.
Hence, we performed an in situ one-pot synthesis of a terbium
complex by stirring a stoichiometric amount of TbCl3·6H2O
and tpy-HImzphen in a chloroform–methanol mixture (1 : 1,
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Dalton Transactions
v/v), followed by the addition of Htta and triethylamine at RT.
The mixture was evaporated to dryness and dissolved in a
small amount of a chloroform/acetonitrile mixture (1 : 1 v/v)
and then the solution was allowed to undergo slow evaporation
for crystallization. Eventually, yellow-coloured single crystals
suitable for X-ray crystallography were obtained after ∼7 days.
The compound [Tb(tta)2(H2O)(tpy-HImzphen)](Cl) (5) crys-
tallizes in the C2/c space group in a monoclinic system. The asym-
metric unit possesses the full molecular structure. The solid-state
structure of the complex is presented in Fig. 5 and the crystallo-
graphic parameters are presented in Table S3, ESI.† Few specific
bond distances and angles of 5 are provided in Table S4, ESI.†
The structural analysis of the complex cation shows that the ter-
pyridine motif of the terpyridyl-imidazole ligands is coordinated
to the TbIII ion in a tridentate fashion, two β-diketonate units of
[tta]−1 are bonded in a bidentate manner as usual and one water
molecule is also coordinated to TbIII completing the eight-coordi-
nation site and depicting distorted square anti-prism geometry.
The Tb–N bond lengths range from 2.495(9) to 2.533(10) Å,
whereas the Tb–O bond lengths range from 2.279(7) to 2.378 Å.
The variation of Tb–O bond lengths reveals that a better overlap
takes place between the [tta−1] groups and the TbIII ion compared
with the water molecule. The bite angles around the TbIII centre
vary between 64.9 and 152.3°.
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Fig. 2 400 MHz 1H NMR spectra of Tb(tta)3(H2O)2 (top) and [Tb(tta)3(tpy-HImzphen)] (4) (bottom) in DMSO-d6.

Fig. 3 MALDI-TOF-MS of Eu(tta)3tpy-HImzphen (2) in dichloromethane solution ( positive mode). The upper right portion shows the experimentally
observed isotopic distribution pattern (a) and the lower right portion shows the simulated isotopic distribution pattern (b).

It is evident that the ligand structure exhibits a strained between the two planes is 31.36°. Moreover, an intermolecular
poly-aromatic system. The phenanthrene moiety is nearly hydrogen bonding is noticed between the hydrogen atom of
coplanar with the imidazole unit, whereas the three pyridine the coordinated water molecule and the imidazole nitrogen of
rings remain almost in another plane. The dihedral angle another moiety [N4–H5B, 2.68 Å; N4–H5B–O5, 74.83°], which

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Fig. 4 Thermogravimetric analysis of all four metal precursors Ln(tta)3(H2O)2 (a) and their corresponding complexes 1–4 (b).

Fig. 5 (a) The solid-state molecular structure of complex 5 (some H atoms are omitted for clarity), (b) intermolecular hydrogen bonding interaction
between two head-to-tail fashioned complex cations with a partial-atom labelling scheme, (c) square anti-prism geometry around the TbIII ion and
(d) coordination polyhedra for the lanthanide core.

may be responsible for the eight-coordinated bis-tta coordi-

nation over the desired nine-coordinated tris-tta coordination.

Photophysical properties
The absorption and emission spectra of the complexes
together with the terpyridyl-imidazole ligand are acquired in
DCM and related spectral profiles are presented in Fig. 6 and
7, while the spectral data are summarized in Table 1. The
absorption peak at 370 nm for the ligand is attributed to the
intra-ligand charge transfer transition (ILCT), while the peak
at 265 nm is due to the π–π* transitions of the aromatic and
heteroaromatic moieties in the ligand. Upon complexation,
the lowest energy absorption peak of the ligand underwent a Fig. 6 Normalized UV-vis absorption spectra of complexes 1–4 along
hypsochromic shift, the extent of which depends on the type with tpy-HImzphen in dry DCM.

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Fig. 7 Luminescence spectra (a, c, e, and g) and lifetime decay plots (b, d, f, and h) of 1–4 at both RT and 77 K.
of lanthanide ion, while the short wavelength peak remained
practically unaffected. The free ligand shows a broad emission
peak at 446 nm.44 In the case of the LaIII complex (1), the said
peak shifts to 505 nm but no emission peak due to an intra-
configurational f–f transition is observed as LaIII possesses no
f-electron (Fig. 7a). The EuIII complex (2), on the other hand,
displays characteristic emission peaks at 579, 592, 614 and
652 nm because of intra-configurational 5D0 → 7F0, 5D0 → 7F1,
5
D0 → 7F2, and 5D0 → 7F3 transitions, respectively (Fig. 7c). The
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peak at 614 nm due to 5D0 → 7F2 transition is the most intense
among the four because of its electric dipole (ED) character. In
addition to its characteristic EuIII-centered emissions, 2 also
exhibits weak ligand-centered emission at 445 nm probably
because of incomplete energy transfer from the ligand to the
EuIII center. In the case of the SmIII complex (3), the ligand-
centered emission peak at 446 nm is found to be predominant,
while the intensities of the SmIII-centered peaks at 564 (5G5/2
→ 5H5/2), 598 (5G5/2 → 5H7/2) and 646 nm (5G5/2 → 5H9/2) are
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Table 1 Photophysical properties of tpy-HImzphen and complexes 1–4 at RT and 77 K
Compounds Absorption, λmax/nm (ε/M−1 cm−1) (×104)
RT tpy-HImzphen 254 (6.5), 343 (2.52), 370 (2.6)
1 261 (7.44), 343 (6.45)
2 261 (9.7), 341 (8.15)
3 261 (8.47), 345 (6.55)
4 262 (7.34), 339 (7.05)
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77 K 1 —
2 —
3 —
4 —
very weak suggesting that the extent of energy transfer between
the tpy-HImzphen ligand and the SmIII center is very small
(Fig. 7e). The TbIII-complex (4), on the other hand, exhibits
only ligand-centered emission at 446 nm with no signature of
characteristic emission peaks for the TbIII center (5D4 → 7FJ,
J=6–3) (Fig. 7g). This is probably due to back energy transfer
from the TbIII center to the ancillary ligand. The relative
quantum yields (Φ) of the complexes (1–4) along with four Ln
(tta)3(H2O)2 precursors are estimated in DCM by using quinine
sulfate as the standard, the details of which are given in the
ESI.† The value of Φ ranges between 3.2% and 78%, depend-
ing on the nature of the lanthanide ion (Table 1). It is to be
noted that the quantum yields of La and Tb complexes are pri-
marily due to ligand fluorescence, while those of Eu and Sm
complexes are due to the summation of both lanthanide-cen-
tered and residual ligand-centered emissions.
The emission lifetimes of the compounds, acquired in
DCM by time correlated single photon counting (TCSPC) or
multi-channel scaling (MCS) methods, are also provided in
Table 1. All the compounds exhibit mono-exponential decay,
as shown in Fig. 7(b, d, f and h). The ligand and complexes 1
and 4 possess RT lifetimes within the domain of 1.9–2.8 ns,
while 2 and 3 are long-lived having lifetimes in the micro-
second domain (73–507 μs; Table 1). The observed lifetimes
suggest that emission in complexes 1 and 4 is primarily due to
radiative deactivation of the ligand-centered excited state,
while that in 2 and 3 is because of the f–f transitions of the
respective lanthanide metal. For the sake of comparison, the
lifetimes of lanthanide precursors, {Ln(tta)3(H2O)2}, are also
measured under similar conditions (Fig. S10, ESI†).
Interestingly, the lifetime of the present Eu-complex (2) (τ =
507 μs) is found to be substantially enhanced compared with
its Eu-tta precursor (τ = 209 μs).
In order to understand the deactivation dynamics of the
excited states of the lanthanide complexes, we also recorded
their steady state luminescence spectra and lifetimes at 77 K.
Associated data and spectra are provided in Table 1 and Fig. 7,
respectively. No significant change is observed for the La-
complex (1) as expected. The ligand-centred emission peak
undergoes only a small blue shift from 470 to 458 nm with
almost no change in its lifetime upon cooling down to 77 K
(Fig. 7a and b). For the EuIII-complex (2), a remarkable
14034 | Dalton Trans., 2023, 52, 14027–14038
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Dalton Transactions
λmax
Ligand centred Metal centred Lifetime (τ) Quantum yield (Φrel/%)
446 — 2.3 ns —
505 — 2.8 ns 78
446 580, 593, 614, 652 507 μs 10
447 565, 598, 646 73 μs 3.2
446 — 1.9 ns 12
458 — 2.36 ns —
429 579, 593, 614, 652 643 μs —
433 562, 597, 644 77 μs —
433 490, 545, 585, 620 621 μs —
increase in the emission intensity of the peak at 614 nm and
its lifetime (507 µs → 643 µs) is observed on passing from RT
to 77 K (Fig. 7d). The SmIII-complex (3) follows the same trend
as that of the EuIII (2) complex, although to a small extent. The
characteristic f–f transition peaks at ∼562 nm, 597 nm and
644 nm get enhanced to some extent along with a small
increase in lifetime (73 µs → 77 µs) (Fig. 7e and f ). The effect
of lowering of temperature is most prominent in the case of
the TbIII-complex (4). The characteristic f–f transition peaks for
5
D4 → 7F6–3 manifolds, which were absent at RT owing to the
thermally-assisted metal-to-ligand back energy transfer, are
restored at 77 K (Fig. 7g). The observed luminescence lifetime
(τ = 621 μs) also confirms that the decay is lanthanide metal-
centric (Fig. 7h).
Photophysics of in situ generated lanthanide(III) complexes
All the four lanthanide complexes (1–4) could also be gener-
ated in situ upon incremental addition of the respective lantha-
nide precursor {Ln(tta)3(H2O)2} to the DCM solution of tpy-
HImzphen. The progress of the formation of the complexes
was monitored through the change in absorption and both
steady-state and time-resolved emission spectroscopic tech-
niques (Fig. 8, 9 and Fig. S11–S15, ESI†). The absorbance of
both ILCT and π–π* absorption bands of the ligand gradually
increases in intensity with the continued addition of the
respective lanthanide precursor, and spectral saturation occurs
upon addition of ∼1 equiv. of {Ln(tta)3(H2O)2}, indicating the
formation of 1 : 1 complexes of the type Ln(tta)3(tpy-
HImzphen). It is to be noted that broad overlapping bands
within the domain of 330–370 nm coalesce into a single band
with its maximum in the ∼340 nm region. We also overlaid the
absorption spectra of the isolated complexes with those of the
in situ generated products at saturation (Fig. S13†). We have
also provided the overlaid absorption spectra for the chromo-
phore, lanthanide precursor and the synthesized complex as
well as the in situ generated complex (all four sets) in the
revised ESI (Fig. S14†). The close similarity of the spectral
pattern clearly indicates the 1 : 1 complex of the lanthanide
precursor {Ln(tta)3(H2O)2} and tpy-HImzphen.
On the emission side, gradual quenching of emission
intensity takes place in all cases and spectral saturation also
occurs upon addition of 1.2 equiv. of {Ln(tta)3(H2O)2}. In the
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Fig. 8 Changes in the (a) absorption and (b) photoluminescence spectra (λex = 370 nm) of ligand tpy-HImzphen upon incremental addition of La
(tta)3(H2O)2 in dry dichloromethane at RT. The inset shows the change of emission color during titration.

Fig. 9 Changes in the (a) absorption and (b) photoluminescence spectra (λex = 370 nm) of ligand tpy-HImzphen upon incremental addition of Eu
(tta)3(H2O)2 in dry dichloromethane at RT. The inset shows the change of emission color during titration.

case of LaIII, the ligand-centered emission gets gradually
quenched together with a red shift of the maximum from
446 nm to 505 nm upon saturation (Fig. 8b). With Eu
(tta)3(H2O)2, systematic quenching of the ligand-centered emis-
sion together with the concomitant emergence of the peaks at
579, 592, 614 and 652 nm due to 5D0 → 7FJ ( J=0–3) transitions is
observed (Fig. 9b). The spectral profile of SmIII is very similar
to that of EuIII, except that the intensities of the newly gener-
ated characteristic emission peaks for SmIII (564, 598 and
646 nm) are lower (Fig. S11, ESI†). In contrast to both EuIII and
SmIII, no signature of characteristic emission peaks for TbIII is
visible during quenching of ligand-centred emission (Fig. S12,
ESI†). It is also observed that the lifetime values at the end of
every titration closely resemble those of the respective isolated
complex, as displayed in Fig. S15, ESI.†
Elucidation of the distinctive responses of four lanthanide
complexes
Since the 4f–4f transitions are both spin and parity (Laporte)
forbidden, direct excitation of the LnIII centers leads to very
weak absorption (ε < 10 M−1 cm−1).32,33,54,55 To circumvent this
disadvantage, light harvesting organic chromophores with high
molar absorption coefficients (ε > 10 000 M−1 cm−1) are intro-
duced here to indirectly sensitize the central lanthanide ion
(antenna effect) for achieving characteristic 4f–4f
emission.6,17,18–22 The most well-accepted energy transfer mecha-
nism for this sort of sensitization involves three steps, viz.
Laporte and spin-allowed ligand absorption and excitation to the
first excited state (S0 → S1), followed by rapid intersystem crossing
to the ligand triplet state (S1 → T1) and finally transferring the
energy from the triplet level of the ligand to the emitting level of
the lanthanide metal ion (T1 → Ln*).1–3,24 The efficacy of the last
step critically depends on the relative positions of both the triplet
level of the ligand (T1) and the lanthanide emitting level (Ln*).
The singlet state lifetime is too short for this energy transfer, yet
this mechanism is also operative.56,57 It has been observed that
both β-diketonate ligands and π-conjugated organic ligands could
effectively sensitize the lanthanide core.35,56,57
It is well known that the lowest-lying emitting excited levels
of EuIII (5D0), SmIII (4G5/2) and TbIII (5D4) reside at ∼17 264,

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Paper
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Fig. 10 Tentative energy transfer mechanism for the lanthanide complexes.
17 900 and 20 500 cm−1, respectively. In order to achieve
effective sensitization, it is postulated that the energy gap
between S1 and T1 of the ligand should be ∼5000 cm−1 (for
effective ISC), while the energy gap between the T1 level of the
ligand and the lowest emitting level of the lanthanide metal
ion (Ln*) should be maintained within 2500–4000 cm−1.2 Now,
we estimated the singlet-state energy level of our ancillary tpy-
HImzphen ligand to be ∼27 027 cm−1 from its absorption
spectrum,58,59 whereas the triplet-state energy level of the
same is ∼20 534 cm−1, obtained from the 77 K phosphor-
escence spectrum of its GdIII analogue (Fig. S16, ESI†).60–63
This positioning of the triplet-state energy level of the ligand is
responsible for the observed variation of the photophysical
properties of the complexes (1–4) compared to their metal pre-
cursors Ln(tta)3·2H2O. Consequently, we observed only a
ligand-centred emission and lifetime value in the case of LaIII
ions as expected. In the case of 2, energy transfer from tpy-
HImzphen to the EuIII-centre takes place quite efficiently,
although it is not as substantial as could be expected from
favourable thermodynamic parameters (good matching of the
ΔE(T1 → Ln*). Although substantial energy transfer takes place
from tpy-HImzphen to EuIII, it is not as great as could be
expected from its favourable energy difference, ΔE(T1 → Ln*).
We are not very sure about the actual reason for this. However,
upon going through the literature on the luminescence charac-
teristics of the related lanthanide complexes, we surmise that
the involvement of a closely associated low-lying ligand-to-
metal charge transfer (LMCT) state is a distinct
possibility.13,64–67 In the case of 3, the relative intensity of the
induced dipole transition for SmIII at 646 nm (5G5/2 → 5H9/2)
together with its lifetime is much less than that of the EuIII
ion. Here also, the extent of energy transfer is much less than
one could anticipate. This could again be attributed to the
presence of a nearby low-lying LMCT state along with multi-
phonon relaxation, as reported in earlier literature studies.2,67
The ΔE(T1 → Ln*) gap in the case of TbIII ions is practically
14036 | Dalton Trans., 2023, 52, 14027–14038
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Dalton Transactions
zero, and it is anticipated that back energy transfer from the
emitting level of the lanthanide metal ion to the triplet energy
level of the ligand(s) (Ln* → T1) takes place wherein the ΔE(T1
→ Ln*) value is less than 1800 cm−1. An energy level diagram
showing the distinctive responses of the four lanthanide com-
plexes is presented in Fig. 10.2,68–70
Conclusions
The primary objective of this work is to incorporate a terpyri-
dyl-imidazole based tridentate ligand into the β-diketonate
lanthanide (III) core for improvement of the photophysical and
particularly the luminescence characteristics of the resulting
lanthanide complexes. To fulfill our objective, we synthesized
four ternary lanthanide tris-(β-diketonate) complexes of the
type [Ln(tta)3(tpy-HImzphen)], where Ln = LaIII, EuIII, SmIII and
TbIII, tta = (2-theonyltrifluoro acetonate) and tpy-HImzphen =
terpyridyl-imidazole based ligand, and thoroughly character-
ized them using standard analytical tools including single
crystal X-ray diffraction. Herein, we restricted our interest to
the above-mentioned four lanthanide ions in terms of having
our facility to measure the photophysical properties in the
visible domain. The photophysical properties of all the com-
plexes were thoroughly investigated via absorption and both
steady-state and time-resolved emission spectroscopic tech-
niques. The emission spectral measurements were carried out
at both room temperature and 77 K to understand the de-
activation dynamics of the excited states and elucidate the dis-
tinctive luminescence responses of the lanthanide complexes.
The LaIII-complex (1) exhibits only ligand-centred emission as
expected as it does not possess any f-electron. For EuIII (2),
efficient energy transfer takes place from tpy-HImzphen to the
EuIII centre which is reflected in its characteristic emission
spectrum peaks due to intraconfigurational 5D0 → 7FJ ( J=0–3)
transitions with concomitant diminution of ligand-centered
This journal is © The Royal Society of Chemistry 2023

Dalton Transactions
emission. The spectral profile of SmIII is very similar to that of
EuIII, except that the intensities of its characteristic emission
peaks are much lower because of the lesser extent of tpy-
HImzphen → SmIII energy transfer. In contrast to both EuIII
and SmIII, no characteristic emission due to 5D4 → 7FJ ( J=6–3)
transitions is observed for TbIII at RT probably because of TbIII
→ tpy-HImzphen back energy transfer. The effect of lowering
of temperature to 77 K is most prominent in the case of the
TbIII complex (4) wherein the characteristic emission peaks
Published on 21 September 2023. Downloaded by Jadavpur University on 11/24/2023 10:39:32 AM.
due to 5D4 → 7FJ ( J=6–3) transitions are observed for the TbIII-
center during systematic quenching of the ligand-centred
emission peak at ∼446 nm. Thus, the present terpyridyl-imid-
azole ligand by virtue of its suitable positioning of the triplet-
state energy level is able to sensitize the lanthanide core quite
efficiently and the extent of sensitization in turn depends on
the nature of the lanthanide ion.
Data availability
Figures and tables related to FT-IR, 1H NMR spectra,
MALDI-TOF, X-ray diffraction study, and absorption and emis-
sion spectra are provided in the attached ESI.†
Author contributions
T. Ahmed and A. Paul carried out the chemical
investigations. A. Chakraborty and T. Ahmed performed data
organization and prepared the draft manuscript. S. Baitalik
supervised and validated this project. The final version of the
manuscript was written by S. Baitalik.
Conflicts of interest
The authors declare no competing financial interest.
Acknowledgements
S. Baitalik acknowledges SERB [grant no. CRG/2020/001233]
and CSIR [Grant No. 01(2945)/18/EMR-II], New Delhi. T. A.
acknowledges CSIR [File No. 09/096(1001)/2019-EMR-I] and A.
C acknowledges D. S. Kothari Post-doctoral Fellowship under
UGC, India [File No. F.4-2/2006(BSR)/CH/20-21/0252] for their
research fellowship.
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